U.S. patent application number 15/501903 was filed with the patent office on 2017-08-10 for polymerizable composition, molded product, and use thereof.
This patent application is currently assigned to Mitsui Chemicals, Inc.. The applicant listed for this patent is Mitsui Chemicals, Inc.. Invention is credited to Dong Gyu JANG, Nobuo KAWATO, Soo Gyun ROH, Naoki SHINOHARA.
Application Number | 20170226267 15/501903 |
Document ID | / |
Family ID | 55263937 |
Filed Date | 2017-08-10 |
United States Patent
Application |
20170226267 |
Kind Code |
A1 |
SHINOHARA; Naoki ; et
al. |
August 10, 2017 |
POLYMERIZABLE COMPOSITION, MOLDED PRODUCT, AND USE THEREOF
Abstract
The polymerizable composition of the present invention includes
at least one isocyanate compound (A) having a cyclic structure,
selected from compounds represented by the following Formulae (1),
(2), and (3), and aliphatic isocyanate compound (B) having 4 to 11
carbon atoms, and a thiol compound (C). ##STR00001##
Inventors: |
SHINOHARA; Naoki;
(Nakano-ku, Tokyo, JP) ; KAWATO; Nobuo;
(Kurume-shi, Fukuoka, JP) ; JANG; Dong Gyu;
(Daejeon, KP) ; ROH; Soo Gyun; (Daejeon,
KP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsui Chemicals, Inc. |
Minato-ku, Tokyo |
|
JP |
|
|
Assignee: |
Mitsui Chemicals, Inc.
Minato-ku, Tokyo
JP
|
Family ID: |
55263937 |
Appl. No.: |
15/501903 |
Filed: |
August 6, 2015 |
PCT Filed: |
August 6, 2015 |
PCT NO: |
PCT/JP2015/072332 |
371 Date: |
February 6, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G02B 1/041 20130101;
G02B 1/04 20130101; C08G 18/751 20130101; G02B 1/14 20150115; C08G
18/722 20130101; C08G 18/735 20130101; C08G 18/724 20130101; C08G
18/38 20130101; C08G 18/752 20130101; C08G 18/74 20130101; C08G
18/7614 20130101; C08G 18/3876 20130101; C08G 18/72 20130101; G02B
1/04 20130101; G02C 7/02 20130101; G02B 1/115 20130101; C08L 75/04
20130101 |
International
Class: |
C08G 18/38 20060101
C08G018/38; G02B 1/04 20060101 G02B001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 7, 2014 |
JP |
2014-161314 |
Oct 7, 2014 |
JP |
2014-206449 |
Claims
1. A polymerizable composition comprising: at least one isocyanate
compound (A) having a cyclic structure, selected from compounds
represented by the following Formulae (1), (2), and (3):
##STR00004## an aliphatic isocyanate compound (B) having 4 to 11
carbon atoms; and a thiol compound (C).
2. The polymerizable composition according to claim 1, wherein the
thiol compound (C) is comprised of at least one selected from
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-bismercaptomethyl-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, ethylene
glycol bis(3-mercaptopropionate), diethylene glycol
bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate),
and diethylene glycol bis(2-mercaptoacetate).
3. The polymerizable composition according to claim 1, wherein the
thiol compound (C) includes an aliphatic polythiol compound having
at least one ester bond within a molecule.
4. The polymerizable composition according to claim 3, wherein the
aliphatic polythiol compound having at least one ester bond within
a molecule is comprised of at least one selected from
pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),
diethylene glycol bis(3-mercaptopropionate), ethylene glycol
bis(2-mercaptoacetate), and diethylene glycol
bis(2-mercaptoacetate).
5. The polymerizable composition according to claim 1, wherein in
the case where the sum of the number of moles of the isocyanate
compound (A) and the number of moles of the isocyanate compound (B)
is taken as 100%, the proportion of the number of moles of the
isocyanate compound (A) is 10% to 95%.
6. A molded product formed by curing the polymerizable composition
according to claim 1.
7. An optical material comprising the molded product according to
claim 6.
8. A lens comprising the optical material according to claim 7.
9. An eyeglass lens comprising the lens according to claim 8.
10. An eyeglass lens comprising: the lens according to claim 8, and
a hard coat layer and/or an antireflection coat layer stacked over
at least one surface of the lens.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polythiourethane-based
polymerizable composition, an optical molded product obtained
therefrom, and use thereof.
BACKGROUND ART
[0002] Plastic lenses have a high refractive index and a high Abbe
number and are light-weight, difficult to crack, and can be dyed as
compared with inorganic lenses. Accordingly, they have been rapidly
spreading as optical materials for eyeglass lenses, camera lenses,
or the like on a commercial scale. Various molded products for
lenses have hitherto been developed and used. A typical example of
these materials may be an optical molded product obtained from a
polymerizable composition including an isocyanate compound and a
thiol compound (Patent Document 1).
[0003] Moreover, for recent eyeglass lenses, there are many cases
where processing for increasing added value is carried out by, for
example, providing a silicon-based hard coat layer on a lens of a
substrate in order to improve hardness; and providing an inorganic
oxide-based antireflection coat layer in order to suppress surface
reflection. On the other hand, impact resistance may be lowered by
providing these coat layers in some cases.
[0004] With a recent spread of sports glasses and children's
glasses, there is a demand for eyeglass lenses having high impact
resistance, such as ones that do not crack even under an impact
when eyeglasses are dropped during heavy exercise or when an object
such as a ball collides with a lens.
[0005] As materials for eyeglass lenses, which have high impact
resistance, polycarbonate or polyureaurethane materials have been
proposed.
[0006] For example, Patent Document 2 discloses that a
polyureaurethane lens including a hard coat layer or an
antireflection coat layer does not crack even when a missile of
1.06 grams collides therewith at a speed of 150 feet in accordance
with the ANSI 287.1 standard, and thus, has very high impact
resistance. However, for the manufacture of the polyureaurethane
lens, it is required to prepare a prepolymer obtained by reacting
an isocyanate component with an alcohol component at a high
temperature 100.degree. C. or more in advance, and a specially
designed molding machine is also required during molding.
Accordingly, the method for manufacturing the lens is very
complicated.
[0007] On the other hand, from the viewpoints that polythiourethane
materials do not require a prepolymerization reaction, and further,
a special molding machine is not required, it is possible to more
conveniently manufacture a lens, as compared with polyureaurethane
materials. Thiourethane-based lenses including a hard coat layer
and an antireflection coat layer, which have improved impact
resistance, have hitherto been proposed (Patent Documents 3 to 7).
These documents disclose a polymerizable composition including a
specific alicyclic isocyanate compound, an aliphatic isocyanate
compound, and a polythiol compound, as a composition for obtaining
a lens substrate.
[0008] In addition, in the case of providing a coat layer on the
surface of a lens, the surface of the lens is subjected to a
surface treatment with an alkaline liquid in advance in some cases.
Due to this alkali treatment, the surface of the lens has white
turbidity or the like in some cases.
[0009] It is an object of the present invention to provide a
polymerizable composition which has high impact resistance as well
as excellent alkali resistance and appearance, as compared with a
polythiourethane-based lens including a hard coat layer and an
antireflection coat layer in the related art, and is capable of
obtaining a lens having excellent impact resistance even in the
case where a primer layer is not disposed between a base layer and
a hard coat layer or antireflection coat layer.
RELATED DOCUMENT
Patent Document
[0010] [Patent Document 1] Japanese Laid-open Patent Publication
No. 63-046213 [0011] [Patent Document 2] WO 2003/044071 [0012]
[Patent Document 3] WO 2008/029994 [0013] [Patent Document 4]
Korean Patent No. 100771176 [0014] [Patent Document 5] Korean
Patent Publication No. 2010/0102987 [0015] [Patent Document 6]
Korean Patent Publication No. 2013/0096507 [0016] [Patent Document
7] WO 2006/109765
SUMMARY OF THE INVENTION
[0017] The present inventors have conducted extensive studies to
solve the problems, and as a result, they have found that a molded
product obtained from a polymerizable composition including a
specific isocyanate compound (A) having a cyclic structure, a
specific aliphatic isocyanate compound (B), and a thiol compound
(C) has excellent impact resistance, an excellent balance among
optical characteristics such as a refractive index and an Abbe
number, handling properties, transparency, and heat resistance, and
excellent alkali resistance, and also has excellent impact
resistance even in the case where the molded product includes a
hard coat layer or an antireflection coat layer, thereby overcoming
the problems, and thus leading to completion of the present
invention.
[0018] Specifically, the present invention is as follows.
[0019] [1] A polymerizable composition including:
[0020] at least one isocyanate compound (A) having a cyclic
structure, selected from compounds represented by the following
Formulae (1), (2), and (3):
##STR00002##
[0021] an aliphatic isocyanate compound (B) having 4 to 11 carbon
atoms; and
[0022] a thiol compound (C).
[0023] [2] The polymerizable composition as described in [1], in
which the thiol compound (C) is comprised of at least one selected
from 4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate),
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-bismercaptomethyl-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, ethylene
glycol bis(3-mercaptopropionate), diethylene glycol
bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate),
and diethylene glycol bis(2-mercaptoacetate).
[0024] [3] The polymerizable composition as described in [1], in
which the thiol compound (C) includes an aliphatic polythiol
compound having at least one ester bond within a molecule.
[0025] [4] The polymerizable composition as described in [3], in
which the aliphatic polythiol compound having at least one ester
bond within a molecule is comprised of at least one selected from
pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),
diethylene glycol bis(3-mercaptopropionate), ethylene glycol
bis(2-mercaptoacetate), and diethylene glycol
bis(2-mercaptoacetate).
[0026] [5] The polymerizable composition as described in any one of
[1] to [4], in which in the case where the sum of the number of
moles of the isocyanate compound (A) and the number of moles of the
isocyanate compound (B) is taken as 100%, the proportion of the
number of moles of the isocyanate compound (A) is 10% to 95%.
[0027] [6] A molded product formed by curing the polymerizable
composition as described in any one of [1] to [5].
[0028] [7] An optical material including the molded product as
described in [6].
[0029] [8] A lens including the optical material as described in
[7].
[0030] [9] An eyeglass lens including the lens as described in
[8].
[0031] [10] An eyeglass lens including the lens as described in
[8], and a hard coat layer and/or an antireflection coat layer
formed on at least one surface of the lens.
[0032] With the polymerizable composition of the present invention,
it is possible to provide a molded product which has excellent
impact resistance, an excellent balance among optical
characteristics such as a refractive index and an Abbe number,
handling properties, transparency, and heat resistance, and
excellent alkali resistance, and also has excellent impact
resistance even in the case where a primer layer is not disposed
between a base layer and a hard coat layer or antireflection coat
layer.
DESCRIPTION OF EMBODIMENTS
[0033] Hereinafter, the present invention will be described in
detail.
[0034] The polymerizable composition of the present invention
contains:
[0035] at least one isocyanate compound (A) having a cyclic
structure, selected from compounds represented by the following
Formulae (1), (2), and (3), an aliphatic isocyanate compound (B)
having 4 to 11 carbon atoms, and a thiol compound (C).
##STR00003##
[0036] Hereinafter, the polymerizable composition of the present
invention will be described with reference to embodiments, but the
present invention is not limited to the exemplified compounds
below. Further, in the present invention, for the respective
components, exemplified compounds may be used alone or in
combination of two or more kinds thereof.
[0037] The isocyanate compound (A) having a cyclic structure in the
present invention is at least one compound selected from compounds
represented by Formula (1), Formula (2), and Formula (3), and
specific examples thereof include
bis(isocyanatomethyl)-bicyclo[2.2.1]heptane,
bis(isocyanatomethyl)cyclohexane, and xylylene diisocyanate, and
the like.
[0038] Among these exemplified compounds, the isocyanate compound
(A) having a cyclic structure is preferably at least one selected
from 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane,
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane,
1,3-bis(isocyanatomethyl)cyclohexane,
1,4-bis(isocyanatomethyl)cyclohexane, and m-xylylene
diisocyanate.
[0039] The aliphatic isocyanate compound (B) having 4 to 11 carbon
atoms in the present invention is a compound which has at least two
isocyanato groups within a molecule and does not include a cyclic
structure or a sulfide bond. Further, the number of carbon atoms
means the number of carbon atoms of an aliphatic group.
[0040] Examples of the aliphatic isocyanate compound (B) having 4
to 11 carbon atoms include tetramethylene diisocyanate,
pentamethylene diisocyanate, hexamethylene diisocyanate,
2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane
diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate,
1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate,
1,8-diisocyanato-4-isocyanatomethyloctane,
bis(isocyanatoethyl)carbonate, and bis(isocyanatoethyl)ether, and
the like.
[0041] Among these exemplified compounds, the aliphatic isocyanate
compound (B) having 4 to 11 carbon atoms is preferably
pentamethylene diisocyanate or hexamethylene diisocyanate.
[0042] Since the polymerizable composition of the present invention
contains the isocyanate compound (A) having a cyclic structure and
the aliphatic isocyanate compound (B) having 4 to 11 carbon atoms,
it is possible to obtain a molded product which has excellent
impact resistance, an excellent balance among optical
characteristics such as a refractive index and an Abbe number,
handling properties, transparency, and heat resistance, and
excellent alkali resistance. Further, it is also possible to obtain
a molded product including a hard coat layer and/or an
antireflection coat layer, which has excellent impact resistance in
a drop ball test in accordance to an FDA test even in the case
where a primer layer is not disposed between a base layer and the
hard coat layer or antireflection coat layer. When the molded
product obtained by curing the polymerizable composition of the
present invention is used, it is not necessary to provide a primer
layer, and therefore, the productivity of the molded product
including these layers is improved.
[0043] In the present invention, in the case where the sum of the
number of moles of the isocyanate compound (A) having a cyclic
structure and the number of moles of the aliphatic isocyanate
compound (B) having 4 to 11 carbon atoms is taken as 100%, the
proportion of the number of moles of the isocyanate compound (A)
having a cyclic structure is 10% to 95%, preferably 30% to 80%,
more preferably 30% to 75%, and still more preferably 30% to 60%.
Within these ranges, a molded product having excellent optical
characteristics such as an Abbe number and a refractive index, an
excellent balance between impact resistance and heat resistance,
and excellent alkali resistance and appearance (transparency) is
obtained. Within these ranges, in the case where the impact
resistance is considered crucial, the proportion is particularly
preferably 30% to 55%, while the heat resistance is considered
crucial, the proportion is particularly preferably 45% to 60%.
Further, even in the case where a primer layer is not disposed
between the base layer and the hard coat layer or antireflection
coat layer, a molded product having excellent impact resistance can
be obtained. That is, within these rages, a balance among these
properties is excellent.
[0044] The polymerizable composition of the present invention may
include an isocyanate compounds other than the isocyanate compound
(A) having a cyclic structure and the aliphatic isocyanate compound
(B) having 4 to 11 carbon atoms, to an extent not impairing the
effects of the present invention.
[0045] Example of the isocyanate compounds other than the
isocyanate compound (A) having a cyclic structure and the aliphatic
isocyanate compound (B) having 4 to 11 carbon atoms include
isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane,
cyclohexane diisocyanate, methylcyclohexane diisocyanate,
2,2-bis(4-isocyanatocyclohexyl)propane,
3,8-bis(isocyanatomethyl)tricyclodecane,
3,9-bis(isocyanatomethyl)tricyclodecane,
4,8-bis(isocyanatomethyl)tricyclodecane,
4,9-bis(isocyanatomethyl)tricyclodecane,
bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,
bis(isocyanatomethyl)naphthalene, naphthalene diisocyanate,
m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, biphenyldiisocyanate,
benzene triisocyanate, bis(isocyanatoethyl)sulfide,
bis(isocyanatopropyl)sulfide, bis(isocyanatomethyl)sulfone,
bis(isocyanatomethyl)disulfide, bis(isocyanatopropyl)disulfide,
bis(isocyanatomethylthio)methane, bis(isocyanatomethylthio)ethane,
bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane,
1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane,
bis(3-isocyanatophenyl)sulfide, bis(4-isocyanatophenyl)sulfide,
bis(3-isocyanatomethylphenyl)sulfide,
bis(4-isocyanatomethylphenyl)sulfide,
bis(3-isocyanatomethylbenzyl)sulfide,
bis(4-isocyanatomethylbenzyl)sulfide,
bis(3-isocyanatophenyl)disulfide, bis(4-isocyanatophenyl)disulfide,
bis(3-isocyanatomethylphenyl)disulfide, and
bis(4-isocyanatomethylphenyl)disulfide, and the like.
[0046] The thiol compound (C) in the present invention is a
compound having two or more mercapto groups within a molecule, and
examples thereof include an aliphatic thiol compound and an
aromatic thiol compound, and the like.
[0047] Examples of the aliphatic thiol compound include
methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol,
1,6-hexanedithiol, 1,2-cyclohexanedithiol,
3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,
1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether,
bis(2-mercaptoethyl)ether, tetrakis(mercaptomethyl)methane,
bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide,
bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide,
bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane,
1,2-bis(mercaptomethylthio)ethane,
1,2-bis(2-mercaptoethylthio)ethane,
1,3-bis(mercaptomethylthio)propane,
1,3-bis(2-mercaptoethylthio)propane,
1,2,3-tris(mercaptomethylthio)propane,
1,2,3-tris(2-mercaptoethylthio)propane,
1,2,3-tris(3-mercaptopropylthio)propane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
tetrakis(mercaptomethylthiomethyl)methane,
tetrakis(2-mercaptoethylthiomethyl)methane,
bis(2,3-dimercaptopropyl)sulfide,
2,5-bismercaptomethyl-1,4-dithiane, ethylene glycol
bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),
diethylene glycol bis(2-mercaptoacetate), diethylene glycol
bis(3-mercaptopropionate),
2,3-dimercapto-1-propanol(3-mercaptopropionate),
3-mercapto-1,2-propane diol bis(2-mercaptoacetate),
3-mercapto-1,2-propane diol di(3-mercaptopropionate),
trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolethane
tris(2-mercaptoacetate), trimethylolethane
tris(3-mercaptopropionate), pentaerythritol
tetrakis(2-mercaptoacetate), pentaerythritol
tetrakis(3-mercaptopropionate), glycerin tris(2-mercaptoacetate),
glycerin tris(3-mercaptopropionate), 1,4-cyclohexane diol
bis(2-mercaptoacetate), 1,4-cyclohexane diol
bis(3-mercaptopropionate), hydroxymethyl sulfide
bis(2-mercaptoacetate), hydroxymethyl sulfide
bis(3-mercaptopropionate), hydroxyethyl sulfide
(2-mercaptoacetate), hydroxyethyl sulfide (3-mercaptopropionate),
hydroxymethyl disulfide (2-mercaptoacetate), hydroxymethyl
disulfide (3-mercaptopropionate), thioglycolic acid
bis(2-mercaptoethylester), and thiodipropionic acid
bis(2-mercaptoethylester), and the like.
[0048] Examples of the aromatic thiol compound include
1,2-dimercaptobenzene, 1,3-dimercaptobenzene,
1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene,
1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene,
1,2,4-tris(mercaptoethyl)benzene, 2,5-toluenedithiol,
3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol,
2,6-naphthalenedithiol, 2,7-naphthalenedithiol,
1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene,
1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(mercaptoethyl)benzene,
1,2,3,5-tetrakis(mercaptoethyl)benzene,
1,2,4,5-tetrakis(mercaptoethyl)benzene, 2,2'-dimercaptobiphenyl,
and 4,4'-dimercaptobiphenyl, and the like.
[0049] Among these exemplified compounds, the aliphatic thiol
compound is preferable, and pentaerythritol
tetrakis(3-mercaptopropionate),
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
2,5-bismercaptomethyl-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane,
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane,
pentaerythritol tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),
diethylene glycol bis(3-mercaptopropionate), ethylene glycol
bis(2-mercaptoacetate), and diethylene glycol
bis(2-mercaptoacetate) are more preferable.
[0050] More preferably, the aliphatic thiol compound includes an
aliphatic polythiol compound having at least one ester bond within
a molecule, and the aliphatic polythiol compound having an ester
bond within a molecule can be used alone or in combination of
another aliphatic thiol compound.
[0051] As the aliphatic polythiol compound having an ester bond
within a molecule, pentaerythritol tetrakis(3-mercaptopropionate),
pentaerythritol tetrakis(2-mercaptoacetate), trimethylolpropane
tris(3-mercaptopropionate), trimethylolpropane
tris(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),
diethylene glycol bis(3-mercaptopropionate), ethylene glycol
bis(2-mercaptoacetate), and diethylene glycol
bis(2-mercaptoacetate) are preferable; pentaerythritol
tetrakis(3-mercaptopropionate) and pentaerythritol
tetrakis(2-mercaptoacetate) are more preferable; and
pentaerythritol tetrakis(3-mercaptopropionate) is particularly
preferable.
[0052] Examples of other aliphatic thiol compounds which can be
used in combination with the aliphatic polythiol compound having an
ester bond within a molecule include the aforementioned aliphatic
thiol compounds, and specifically,
[0053] 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
2,5-bismercaptomethyl-1,4-dithiane,
1,1,3,3-tetrakis(mercaptomethylthio)propane,
4,6-bis(mercaptomethylthio)-1,3-dithiane, and
2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane are
preferable, and
[0054] 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane are
particularly preferable.
[0055] It is particularly preferable from the viewpoints of the
aforementioned effects that the polymerizable composition of the
present embodiment includes a combination of the compound
represented by Formula (1), Formula (2), or Formula (3) as the
isocyanate compound (A) having a cyclic structure, hexamethylene
diisocyanate as the aliphatic isocyanate compound (B) having 4 to
11 carbon atoms, and pentaerythritol tetrakis(3-mercaptopropionate)
as the thiol compound (C).
[0056] In the present invention, the molar ratio of the mercapto
groups in the thiol compound (C) with respect to the total amount
of the isocyanato groups in the isocyanate compound (A) having a
cyclic structure, the aliphatic isocyanate compound (B) having 4 to
11 carbon atoms, and the isocyanate compound other than (A) and
(B), added as necessary, is in the range of 0.8 to 1.2, preferably
in the range of 0.85 to 1.15, and more preferably 0.9 to 1.1.
Within the ranges, a molded product which is suitably used as an
optical material, in particular, a plastic lens material for
eyeglasses can be obtained.
[0057] Moreover, it is possible to add a modifier to the
polymerizable composition of the present invention within a range
not impairing the effects of the present invention, for the
purposes of adjusting various properties such as optical
properties, impact resistance, and specific gravity of the obtained
molded product, and of adjusting the handling properties of the
respective components in the polymerizable composition.
[0058] Examples of the modifier include an episulfide compound, an
alcohol compound, an amine compound, an epoxy compound, an organic
acid and an anhydride thereof, and olefin compounds including a
(meth)acrylate compound. A case where a hydroxyl group is not
included is preferable from the viewpoints of occurrence of
irregularities during polymerization of a lens, and dyeing
properties.
[0059] In the present invention, when the polythiourethane
polymerizable composition is molded, depending on purposes,
similarly to well-known molding methods, various additives such as
a catalyst, an internal releasing agent, a chain extender, a
crosslinking agent, a light stabilizer, an ultraviolet ray
absorber, an antioxidant, a coloration inhibitor, an oil-soluble
dye, a filler, and an adhesion improver may be added.
[0060] Examples of the catalyst include a Lewis acid, an amine, an
organic acid, and an amine organic acid salt, among which the Lewis
acid, the amine, and the amine organic acid salt are preferable,
and dimethyl tin chloride, dibutyl tin chloride, dibutyl tin
laurate are more preferable. The addition amount thereof is
preferably from 0.005 parts by weight to 0.5 parts by weight, and
more preferably from 0.005 parts by weight from 0.3 parts by
weight, with respect to 100 parts by weight of the total amount of
the isocyanate (A), the isocyanate (B), and the thiol (C).
[0061] As the internal releasing agent, an acidic phosphoric acid
ester can be used. Examples of the acidic phosphoric acid ester
include a phosphoric acid monoester and a phosphoric acid diester,
and these may be used singly or in mixture of two or more kinds
thereof.
[0062] In the case where a polymerizable composition is prepared by
mixing isocyanate compound (A) having a cyclic structure, the
aliphatic isocyanate compound (B) having 4 to 11 carbon atoms, and
the thiol compound (C), and other components as necessary, a
catalyst, an internal releasing agent, and other additives, the
mixing is usually carried out at a temperature 25.degree. C. or
lower. In some cases, a lower temperature is more preferable in
terms of the pot life of the polymerizable composition. However, in
the case where the solubility of the catalyst, the internal
releasing agent, and the additives in the polymerizable composition
or the like is not favorable, it is also possible to dissolve the
catalyst, the internal releasing agent, and the additives in the
polymerizable composition, the modifier, or the like by warming the
catalyst, the internal releasing agent, and the additive in
advance.
[0063] In the present invention, a method for preparing a
polythiourethane molded product is not particularly limited, but
preferable examples of the preparation method include cast
polymerization. First, the polymerizable composition is injected
into a mold held using a gasket, a tape, or the like. At this time,
there are many cases in which a degassing treatment under reduced
pressure, a filtration treatment under pressure or reduced pressure
are preferably carried out, as necessary, depending on the
properties required for the obtained plastic lenses.
[0064] Since polymerization conditions significantly vary depending
on the kinds and amounts of the polymerizable composition and the
catalyst used, the shape of the mold, and the like, the
polymerization conditions are not limited, but polymerization is
carried out at a temperature of approximately -50.degree. C. to
150.degree. C. for 1 to 50 hours. The polymerizable composition is
preferably held in a temperature range of 5.degree. C. to
150.degree. C. or slowly warmed, and cured, but the temperature may
be suitably adjusted.
[0065] The polythiourethane molded product of the present invention
may be subjected to an annealing treatment and the like, as
necessary. The treatment temperature is usually 50 to 150.degree.
C., but is preferably 90 to 140.degree. C., and more preferably 100
to 130.degree. C.
[0066] Molded products having various shapes can be obtained from
the polythiourethane polymerizable composition of the present
invention by changing molds during cast polymerization. The molded
product of the present invention can be used as various optical
materials by forming them into desired shapes and incorporating
coating layers formed, as necessary, other members, and the
like.
[0067] The molded product obtained by curing the polymerizable
composition of the present invention has a high refractive index
and high transparency, and can be used for optical molded products
such as eyeglass lenses, camera lenses, light emitting diodes
(LED), prisms, optical fibers, information recording substrates,
filters, and light-emitting diodes, and in optical materials
therefor. The molded product is particularly suitable as optical
materials of lenses such as eyeglass lenses and camera lenses, and
of light emitting diodes.
[0068] The molded product obtained by curing the polymerizable
composition of the present invention may be provided with a coating
layer over a single surface or both surfaces as necessary, and then
used. Examples of the coating layer include a hard coat layer, an
antireflection film layer, an antifog coated film layer, an
antifouling layer, a water repellent layer, a primer layer, and a
photochromic layer, and the like. These coating layers may be used
singly or as a multilayered body formed of a plurality of the
coating layers. In the case where the coating layers are formed
over both surfaces, the same coating layers may be provided over
the respective surfaces or different coating layers may be
provided.
[0069] The eyeglass lens of the present invention may include a
hard coat layer and/or an antireflection coat layer formed over at
least one surface of a molded product (lens) obtained by curing the
polymerizable composition of the present invention. Further, the
eyeglass lens may also include layers other than the above layer
(s). Since the eyeglass lens of the present invention uses a lens
including the polymerizable composition of the present invention,
then even in the case where a primer layer is not disposed between
the base layer and the hard coat layer or antireflection coat
layer, the impact resistance is excellent. That is, in the present
embodiment, a hard coat layer and/or an antireflection coat layer
may be directly formed over at least one surface of the base layer.
By using the molded product obtained by curing the polymerizable
composition of the present invention as a substrate of a lens, it
is not necessary to provide a primer layer, and therefore, the
productivity of the eyeglass lens is improved.
[0070] The hard coat layer is provided over at least one surface of
a molded product (lens) obtained by curing the polymerizable
composition of the present invention, and is a coating layer aiming
to impart scratch resistance, wear resistance, humidity resistance,
hot water resistance, heat resistance, light resistance, and the
like to the surface of the lens. The hard coat layer is obtained
from a composition containing at least one oxide of metal selected
from an element group of silicon, zirconium, antimony, tin,
aluminum, tungsten, and antimony, a silane compound having at least
one functional group selected from an alkyl group, an aryl group,
an alkoxy group, a methacryloxy group, an acryloxy group, an epoxy
group, an amino group, an isocyanato group, and a mercapto group,
and a hydrolysate thereof.
[0071] A curing agent may be included in the hard coat composition
for the purpose of accelerating the curing. Specific examples of
the curing agent include inorganic acids, organic acids, amines,
metal complexes, organic acid metal salts, and metal chlorides. For
the preparation of the hard coat composition, a solvent may be
used. Specific examples of the solvent include water, alcohols,
ethers, ketones, and esters.
[0072] The hard coat layer is formed by coating the hard coating
composition onto the surface of the molded product, using a
well-known coating method such as spin coating and dip coating.
Examples of the curing method include curing methods using thermal
curing or radiation of energy rays such as ultraviolet rays and
visible light rays. In the case of heating and curing, the heating
and the curing are preferably carried out at 80.degree. C. to
120.degree. C. for 1 to 4 hours. In order to suppress the
generation of interference fringes, the refractive index of the
hard coat layer is preferably within the range of a difference in
the refractive index of the molded product of .+-.0.1.
[0073] Before applying the hard coat layer, the surface of the
substrate is preferably subjected to ultrasonic washing with an
aqueous alkali solution so as to satisfy the following conditions
(a) to (d):
[0074] (a) the aqueous alkali solution is a 5% to 40% aqueous
sodium hydroxide or potassium hydroxide solution,
[0075] (b) the treatment temperature of the aqueous alkali solution
is 30.degree. C. to 60.degree. C.,
[0076] (c) the treatment time is 3 to 5 minutes, and
[0077] (d) the frequency of the ultrasonic wave is 20 to 30
kHz.
[0078] After washing with an aqueous alkali solution, the substrate
may be washed with alcohols such as distilled water and
isopropanol, or the like and may be dried the surface of the molded
product in the range of 50.degree. C. to 80.degree. C. for 5
minutes to 20 minutes.
[0079] The molded product obtained from the polymerizable
composition of the present invention has excellent alkali
resistance, and even after washing with an aqueous alkali solution,
occurrence of white turbidity or the like is suppressed.
[0080] The antireflection layer is a coating layer in which a
molded product (lens) is provided on at least surface thereof, and
has a purpose of lowering the reflection rate generated from the
difference in the refractive index between air and the molded
product and significantly reducing the reflection of light on the
surface of the plastic lens to increase the transmittance. The
antireflection layer in the present embodiment includes a
low-refractive index film layer containing silicon oxide, and a
high-refractive index film layer containing at least one metal
oxide selected from titanium oxide, zirconium oxide, aluminum
oxide, zinc oxide, cerium oxide, antimony oxide, tin oxide, and
tantalum oxide, and each of the layers may be a monolayer or
multilayer structure.
[0081] In the case where the antireflection layer is a multilayer
structure, 5 to 7 layers are preferably laminated. The film
thickness is preferably 100 to 300 nm, and more preferably 150 to
250 nm. Examples of the method for forming the multilayer
antireflection layer include a vacuum deposition method, a
sputtering method, an ion plating method, an ion beam assisting
method, and a CVD method.
[0082] The antifog coated film layer, the antifouling layer, and
the water repellent layer may be formed on the antireflection film
layer, as necessary. Regarding a method for forming the antifog
coated layer, the antifouling layer, and the water repellent layer,
the treatment method, the treatment materials, and the like
therefor are not particularly limited as long as no adverse
influences are brought to the antireflection function, and
well-known antifog coating treatment methods, antifouling treatment
methods, water repellent treatment methods, and materials can be
used. Examples of the antifog coating method and the antifouling
treatment method include a method in which the surface is covered
with a surfactant, a method in which a hydrophilic film is added to
the surface so as to provide water absorbability, a method in which
the surface is coated with fine irregularity so as to enhance water
absorbability, a method in which a photocatalytic activity is used
so as to provide water absorbability, a method in which a super
water repellent treatment is carried out so as to prevent
attachment of water droplets, and the like. In addition, examples
of the water repellent treatment method include a method in which a
water repellency-provided layer is formed using a
fluorine-containing silane compound or the like by deposition or
sputtering, and a method in which a fluorine-containing silane
compound is dissolved in a solvent and then coated so as to form a
water repellency-treated layer.
[0083] An ultraviolet ray absorber for protecting lenses or eyes
from ultraviolet rays, an infrared ray absorber for protecting the
eyes from infrared rays, a light stabilizer or antioxidant for
improving the weather resistance of lenses, a dye or pigment for
enhancing the aesthetic appearance of lenses, a photochromatic dye
or photochromatic pigment, an antistatic agent, or other known
additives for enhancing the performance of lens may also be used in
combination with other components. For the layer in which coating
is performed by application, various leveling agents for improving
the coatability may also be used.
[0084] The plastic lenses using the polythiourethane polymerizable
composition of the present invention aims to impart, for example,
aesthetic appearance or photochromatic properties, and may also be
used after being dyed using a dye depending on purposes. The dyeing
of lenses can be carried out using a known dyeing method, but is
usually carried out by the method shown below.
[0085] Generally, the method involves immersing a lens fabric
prepared on a predetermined optical surface in a dyeing solution in
which a pigment to be used is dissolved or homogeneously dispersed
(dyeing step), and then heating the lens as necessary so as to fix
the pigment (annealing-after-dyeing step). The dye used in the
dyeing step is not particularly limited as long as the pigment is a
known pigment, and generally, an oil-soluble dye or dispersion dye
is used. The solvent used in the dyeing step is not particularly
limited as long as the solvent can dissolve or homogeneously
disperse the pigment to be used. In the dyeing step, a surfactant
for dispersing the pigment in the dyeing solution or a carrier for
accelerating dyeing may be added as necessary.
[0086] In the dyeing step, a pigment, and a surfactant which is
added as necessary are dispersed in water or a mixture of water and
an organic solvent so as to prepare a dyeing bath, an optical lens
is immersed in the dyeing bath, and dyed at a predetermined
temperature for a predetermined period. The dyeing temperature and
period vary depending on a desired dyeing concentration, but in
general, dyeing may be carried out at a temperature equal to or
lower than 120.degree. C. for approximately several minutes to
several tens of hours, and the dyeing concentration of the dyeing
bath is 0.01 to 10% by weight. In addition, in the case where it is
difficult to perform dyeing, dyeing may be carried out under
pressurization.
[0087] The annealing-after-dyeing step which is carried out as
necessary is a step in which a heating treatment is carried out on
a dyed lens fabric. In the heating treatment, water remaining on
the surface of the lens fabric dyed in the dyeing step is removed
using a solvent or the like, or the solvent is dried using wind,
and then the lens fabric is held in a furnace, such as an infrared
ray heating furnace under the atmosphere or a resistance heating
furnace, for a predetermined period. In the annealing-after-dyeing
step, bleaching of the dyed lens fabric is prevented
(bleaching-prevention treatment), and moisture which has intruded
into the lens fabric during dyeing is removed. In the present
invention, in the case where an alcohol compound is not included,
the irregularities after dyeing are little.
[0088] In the present invention, a polarizing lens can be obtained
by laminating a molded product obtained by curing the polymerizable
composition of the present invention over at least one surface of a
polarizing film. The preparation method is not particularly
limited, and a well-known method can be employed. Examples of the
polarizing film include thermoplastic polyesters such as
polyethylene terephthalate, and polyvinyl alcohol.
[0089] Aspects of the present invention are described above, but
various aspects can be employed within a range not impairing the
effects of the present invention.
EXAMPLES
[0090] Hereinafter, the present invention will be specifically
described based on Examples, but the present invention is not
limited these Examples. In the performance tests of the molded
product obtained by curing the polymerizable composition of the
present invention, the refractive indexes, the Abbe numbers, the
specific gravities, the heat resistance, and the impact resistance
were evaluated using the following methods.
[0091] Refractive indexes (ne) and Abbe numbers (.nu.e): Measured
at 20.degree. C. using a PULFRICH refractometer.
[0092] Specific gravities: Measured using an Archimedes method.
[0093] Heat resistance: The glass transition temperature was
measured using a TMA penetration method (50 g of a load, 0.5
mm.phi. at the tip of a pin, and a temperature-rise rate of
10.degree. C./min).
[0094] Impact resistance: Using an automatic drop weight impact
test machine "HYDROSHOT" (Model HITS-P10) manufactured by Shimadzu
Corporation, the manufactured molded product was fixed to a
pedestal with a diameter of 40 mm in accordance with JIS K7211-2, a
striker having a diameter of 20 mm was collided and penetrated at a
speed of 4.4 m/sec, and the fracture energy (J) generated at the
time of impact was calculated. Three molded products were tested
and an average value of the three products with the fracture energy
was calculated. Further, the shape of the molded product used in
the measurement is a 4 curve shape having a thickness of 2 mm and a
diameter of 75 mm, and has a hard coat layer and an antireflection
layer.
[0095] Drop ball test: For the lenses each having a shape of a
central thickness of 1.1 mm to 1.2 mm, a diameter of 75 mm, and
S=-1.75D, in which a hard coat layer and an antireflection layer
were stacked, 11 kinds of iron balls having different weights of 8
g, 16 g, 28 g, 33 g, 45 g, 67 g, 95 g, 112 g, 174 g, 226 g, and 534
g were dropped in this order onto the center of the lens from the
position at a height of 127 cm (50 inches), and it was tested
whether the lenses were damaged. For evaluation, the tests were
carried out on five lenses and the maximum weight when not even one
lens was damaged was recorded.
[0096] Alkali test: A lens having a shape of a central thickness of
1.1 mm to 1.2 mm, a diameter of 75 mm, and S=-1.75D was immersed in
a 15% aqueous potassium hydroxide solution warmed at 60.degree. C.
After the immersion, the lens was subjected to an ultrasonic
treatment and taken up every 10 minute to observe the presence or
absence of white turbidity in the lens. In observation after 30
minutes, presence of white turbidity in the lens was denoted by x
and absence of white turbidity in the lens was denoted by O.
[0097] Appearance: The appearance of the lenses immediately after
the release was observed under irradiation with a high-pressure
mercury lamp. A case with no turbidity in the lens was denoted by
.degree. and a case with turbidity in the lens was denoted by
x.
Example 1
[0098] 16.8 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 25.8 parts by
weight of hexamethylene diisocyanate, 57.4 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 0.05 parts by
weight of dibutyl tin dichloride, 2.0 parts by weight of an
ultraviolet ray absorber (manufactured by Kyodo Chemical Co., Ltd.,
product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0099] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0100] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 41, a specific gravity of 1.29, and a heat resistance of
81.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0101] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 10.6 J. The lens
was subjected to a drop ball test, and thus, even when 534 g of an
iron ball was dropped, the lens was not damaged. The evaluation
results are shown in Table-1.
Example 2
[0102] 23.9 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 19.5 parts by
weight of hexamethylene diisocyanate, 56.6 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 0.05 parts by
weight of dibutyl tin dichloride, 2.0 parts by weight of an
ultraviolet ray absorber (manufactured by Kyodo Chemical Co., Ltd.,
product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0103] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0104] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 41, a specific gravity of 1.30, and a heat resistance of
87.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0105] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 6.2 J. The lens
was subjected to a drop ball test, and thus, even when 534 g of an
iron ball was dropped, the lens was not damaged. The evaluation
results are shown in Table-1.
Example 3
[0106] 22.0 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 27.0 parts by
weight of hexamethylene diisocyanate, 16.3 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 34.7 parts by
weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 0.10
parts by weight of dibutyl tin dichloride, 1.2 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0107] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0108] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.60, an Abbe number (.nu.e)
of 39, a specific gravity of 1.29, and a heat resistance of
83.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0109] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 11.2 J. The lens
was subjected to a drop ball test, and thus, even when 534 g of an
iron ball was dropped, the lens was not damaged. The evaluation
results are shown in Table-1.
Example 4
[0110] 29.9 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 19.9 parts by
weight of hexamethylene diisocyanate, 16.0 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 34.2 parts by
weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 0.10
parts by weight of dibutyl tin dichloride, 1.2 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0111] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0112] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.60, an Abbe number (.nu.e)
of 39, a specific gravity of 1.30, and a heat resistance of
91.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0113] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 4.4 J. The lens
was subjected to a drop ball test, and thus, even when 534 g of an
iron ball was dropped, the lens was not damaged. The evaluation
results are shown in Table-1.
Example 5
[0114] 35.8 parts by weight of m-xylylene diisocyanate, 7.7 parts
by weight of hexamethylene diisocyanate, 56.5 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 0.01 parts by
weight of dibutyl tin dichloride, 1.5 parts by weight of an
ultraviolet ray absorber (manufactured by Kyodo Chemical Co., Ltd.,
product name: VIOSORB 583), and 0.10 parts by weight of an internal
releasing agent (acidic phosphoric acid ester, manufactured by
Mitsui Chemicals, Inc., product name: Internal Releasing Agent for
MR) were mixed and dissolved to produce a homogeneous solution.
This mixed solution was degassed at 400 Pa for 1 hour, then
filtered using a 1 .mu.m PTFE-made filter, and injected into a mold
composed of a glass mold and a tape. The mold was put into a
polymerization oven and slowly heated from 25.degree. C. to
120.degree. C. for 21 hours so as to perform polymerization. After
the completion of polymerization, the mold was removed from the
oven. The release properties of a molded product from the mold were
good. The obtained molded product was further subjected to an
annealing treatment at 130.degree. C. for 2 hours.
[0115] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0116] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.59, an Abbe number (.nu.e)
of 35, a specific gravity of 1.32, and heat resistance of
85.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0117] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 14.0 J. The
evaluation results are shown in Table-1.
Example 6
[0118] 16.0 parts by weight of
1,3-bis(isocyanatomethyl)cyclohexane, 26.0 parts by weight of
hexamethylene diisocyanate, 58.0 parts by weight of pentaerythritol
tetrakis(3-mercaptopropionate), 0.05 parts by weight of dibutyl tin
dichloride, 1.5 parts by weight of an ultraviolet ray absorber
(manufactured by Kyodo Chemical Co., Ltd., product name: VIOSORB
583), and 0.065 parts by weight of an internal releasing agent
(acidic phosphoric acid ester, manufactured by Mitsui Chemicals,
Inc., product name: Internal Releasing Agent for MR) were mixed and
dissolved to produce a homogeneous solution. This mixed solution
was degassed at 400 Pa for 1 hour, then filtered using a 1 .mu.m
PTFE-made filter, and injected into a mold composed of a glass mold
and a tape. The mold was put into a polymerization oven and slowly
heated from 25.degree. C. to 120.degree. C. for 21 hours so as to
perform polymerization. After the completion of polymerization, the
mold was, removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0119] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0120] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 41, a specific gravity of 1.28, and heat resistance of
77.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0121] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 10.5 J. The
evaluation results are shown in Table-1.
Example 7
[0122] 16.0 parts by weight of
1,4-bis(isocyanatomethyl)cyclohexane, 26.0 parts by weight of
hexamethylene diisocyanate, 58.0 parts by weight of pentaerythritol
tetrakis(3-mercaptopropionate), 0.05 parts by weight of dibutyl tin
dichloride, 1.5 parts by weight of an ultraviolet ray absorber
(manufactured by Kyodo Chemical Co., Ltd., product name: VIOSORB
583), and 0.065 parts by weight of an internal releasing agent
(acidic phosphoric acid ester, manufactured by Mitsui Chemicals,
Inc., product name: Internal Releasing Agent for MR) were mixed and
dissolved to produce a homogeneous solution. This mixed solution
was degassed at 400 Pa for 1 hour, then filtered using a 1 .mu.m
PTFE-made filter, and injected into a mold composed of a glass mold
and a tape. The mold was put into a polymerization oven and slowly
heated from 25.degree. C. to 120.degree. C. for 21 hours so as to
perform polymerization. After the completion of polymerization, the
mold was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0123] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0124] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 41, a specific gravity of 1.29, and heat resistance of
82.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0125] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 10.9 J. The
evaluation results are shown in Table-1.
Example 8
[0126] 16.4 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 31.2 parts by
weight of hexamethylene diisocyanate, 16.2 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 36.2 parts by
weight of a mixture of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 0.10
parts by weight of dibutyl tin dichloride, 1.2 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0127] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0128] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.61, an Abbe number (.nu.e)
of 40, a specific gravity of 1.30, and heat resistance of
88.degree. C., and was thus suitable as an optical material.
Further, the molded product was subjected to an alkali test, and
thus, a deterioration such as white turbidity was not observed even
after 30 minutes have passed in the lens. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0129] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 4.3 J. The
evaluation results are shown in Table-1.
Comparative Example 1
[0130] 15.5 parts by weight of isophorone diisocyanate, 27.5 parts
by weight of hexamethylene diisocyanate, 57.0 parts by weight of
pentaerythritol tetrakis(3-mercaptopropionate), 0.17 parts by
weight of dibutyl tin dichloride, 2.0 parts by weight of an
ultraviolet ray absorber (manufactured by Kyodo Chemical Co., Ltd.,
product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0131] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0132] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 41, a specific gravity of 1.26, and heat resistance of
82.degree. C. Further, the molded product was subjected to an
alkali test, and thus, white turbidity of the lens was observed
after 30 minutes have passed. In addition, the appearance of the
lens immediately after release was observed under irradiation with
a high-pressure mercury lamp or the like, and thus, turbidity was
observed.
[0133] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 4.9 J. The
evaluation results are shown in Table-2.
Comparative Example 2
[0134] 23.4 parts by weight of bis(4-isocyanatocyclohexyl)methane,
22.4 parts by weight of hexamethylene diisocyanate, 54.2 parts by
weight of pentaerythritol tetrakis(3-mercaptopropionate), 0.17
parts by weight of dibutyl tin dichloride, 2.0 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.065 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0135] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0136] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.56, an Abbe number (.nu.e)
of 42, a specific gravity of 1.26, and heat resistance of
85.degree. C. Further, the molded product was subjected to an
alkali test, and thus, white turbidity of the lens was observed
after 30 minutes have passed. In addition, the appearance of the
lens immediately after release was observed under irradiation with
a high-pressure mercury lamp or the like, and thus, turbidity was
observed.
[0137] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 3.6 J. The
evaluation results are shown in Table-2.
Comparative Example 3
[0138] 45.9 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 54.1 parts by
weight of pentaerythritol tetrakis(3-mercaptopropionate), 0.03
parts by weight of dimethyl tin dichloride, 1.5 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.10 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0139] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0140] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.57, an Abbe number (.nu.e)
of 42, a specific gravity of 1.31, and heat resistance of
111.degree. C. Further, the molded product was subjected to an
alkali test, and thus, changes such as white turbidity of the lens
was not observed after 30 minutes have passed. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed. In addition, the coat
layer-attached lens was subjected to an impact resistance test in
accordance with JIS K7211-2 to calculate a fracture energy, which
was found to be 0.5 J. The evaluation results are shown in
Table-2.
Comparative Example 4
[0141] 54.3 parts by weight of a mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 45.7 parts by
weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 0.05
parts by weight of dimethyl tin dichloride, 1.5 parts by weight of
an ultraviolet ray absorber (manufactured by Kyodo Chemical Co.,
Ltd., product name: VIOSORB 583), and 0.10 parts by weight of an
internal releasing agent (acidic phosphoric acid ester,
manufactured by Mitsui Chemicals, Inc., product name: Internal
Releasing Agent for MR) were mixed and dissolved to produce a
homogeneous solution. This mixed solution was degassed at 400 Pa
for 1 hour, then filtered using a 1 .mu.m PTFE-made filter, and
injected into a mold composed of a glass mold and a tape. The mold
was put into a polymerization oven and slowly heated from
25.degree. C. to 120.degree. C. for 21 hours so as to perform
polymerization. After the completion of polymerization, the mold
was removed from the oven. The release properties of a molded
product from the mold were good. The obtained molded product was
further subjected to an annealing treatment at 130.degree. C. for 2
hours.
[0142] After the annealing treatment, the molded product was washed
with a 10% aqueous potassium hydroxide solution in an ultrasonic
washing bath at 50.degree. C. for 5 minutes. Thereafter, the molded
product was washed with distilled water and isopropanol, and the
surface of the lens was dried at 50.degree. C. The washed molded
product was immersed in a hard coat composition containing silicon
oxide, trimethoxymethylsilane and a hydrolysate thereof, taken up
at a speed of 150 mm/min to coat the molded product. Thereafter,
the molded product was preheated at 80.degree. C. for 10 minutes,
and then heated and cured at 110.degree. C. for 2 hours to form a
hard coat layer. A multilayered antireflection layer with five
layers, including silicon oxide/zirconium oxide was formed on the
molded product provided with a hard coat layer, using a vacuum
deposition device, thereby obtaining a coat layer-attached
lens.
[0143] Furthermore, the obtained molded product was transparent,
coloration of the molded product was not observed, and the molded
product had a refractive index (ne) of 1.62, an Abbe number (.nu.e)
of 39, a specific gravity of 1.31, and heat resistance of
116.degree. C. Further, the molded product was subjected to an
alkali test, and thus, changes such as white turbidity of the lens
was not observed after 30 minutes have passed. In addition, the
appearance of the lens immediately after release was observed under
irradiation with a high-pressure mercury lamp or the like, and
thus, turbidity was not observed.
[0144] In addition, the coat layer-attached lens was subjected to
an impact resistance test in accordance with JIS K7211-2 to
calculate a fracture energy, which was found to be 0.4 J. The
evaluation results are shown in Table-2.
TABLE-US-00001 TABLE 1 Molar ratio Refractive Abbe Heat Impact
Component Component (component Component index number resistance
Specific resistance Alkali Appear- A B A:component B) C (ne) (ve)
(.degree. C.) gravity (J) test ance Example 1 i-1 i-2 34:66 t-1 --
1.56 41 81 1.29 10.6 .largecircle. .largecircle. Example 2 i-1 i-2
50:50 t-1 -- 1.56 41 87 1.30 6.2 .largecircle. .largecircle.
Example 3 i-1 i-2 40:60 t-1 t-2 1.60 39 83 1.29 11.2 .largecircle.
.largecircle. Example 4 i-1 i-2 55:45 t-1 t-2 1.60 39 91 1.30 4.4
.largecircle. .largecircle. Example 5 i-3 i-2 80:20 t-1 -- 1.59 35
85 1.32 14.0 .largecircle. .largecircle. Example 6 i-4 i-2 35:65
t-1 -- 1.56 41 77 1.28 10.5 .largecircle. .largecircle. Example 7
i-5 i-2 35:65 t-1 -- 1.56 41 82 1.29 10.9 .largecircle.
.largecircle. Example 8 i-1 i-2 30:70 t-1 t-3 1.61 40 88 1.30 4.3
.largecircle. .largecircle.
TABLE-US-00002 TABLE 2 Molar ratio Refractive Abbe Heat Impact
Component Component (component Component index number resistance
Specific resistance Alkali Appear- A B A:component B) C (ne) (ve)
(.degree. C.) gravity (J) test ance Comparative i-6 i-2 30:70 t-1
1.56 41 82 1.26 4.9 X X Example 1 Comparative i-7 i-2 40:60 t-1
1.56 42 85 1.26 3.6 X X Example 2 Comparative i-1 -- 100:0 t-1 1.57
42 111 1.31 0.5 .largecircle. .largecircle. Example 3 Comparative
i-1 -- 100:0 t-2 1.62 39 116 1.31 0.4 .largecircle. .largecircle.
Example 4
[0145] 1-1: A mixture of
2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane
[0146] i-2: Hexamethylene diisocyanate
[0147] i-3: m-Xylylene diisocyanate
[0148] i-4: 1,3-Bis(isocyanatomethyl)cyclohexane
[0149] i-5: 1,4-Bis(isocyanatomethyl)cyclohexane
[0150] i-6: Isophorone diisocyanate
[0151] i-7: Bis(4-isocyanatocyclohexyl)methane
[0152] t-1: Pentaerythritol tetrakis(3-mercaptopropionate)
[0153] t-2: 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
[0154] t-3: A mixture of
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
[0155] From the above results, it was found that a molded product
obtained from the polymerizable composition of the present
invention has improved impact resistance and alkali resistance, as
compared with Comparative Examples.
[0156] By the polymerizable composition of the present invention, a
molded product or an optical material, having excellent impact
resistance and alkali resistance, is obtained. Further, the optical
material obtained from the polymerizable composition of the present
invention also has an excellent balance among optical
characteristics such as a refractive index and an Abbe number,
handling properties, transparency, and heat resistance.
[0157] Such a polymerizable composition can be suitably used as a
molded product for an optical material which requires a high
refractive index, high impact resistance, and alkali resistance,
and in particular, in a plastic lens for eyeglasses.
[0158] The present application claims priority based on Japanese
Patent Application No. 2014-161314, filed on Aug. 7, 2014, and
Japanese Patent Application No. 2014-206449, filed on Oct. 7, 2014,
the contents of which are incorporated herein by reference.
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